WO2019066204A1 - Polyimide precursor solution and polyimide film produced using same - Google Patents

Abstract

The present invention relates to the production of a polyimide precursor, whereby, by using an amide-based organic solvent having a positive-number partition coefficient (LogP) and a density of at most 1 g/cm3, an interaction between the organic solvent and polyamic acid, which is a polyimide precursor, may be mitigated, thereby enabling the decrease of the viscosity of a polyimide precursor solution, and thus enabling a polyimide precursor solution having high solid content and low viscosity to be obtained.

Description

A polyimide precursor solution and a polyimide film produced therefrom

The present application is filed on September 29, Korean Patent Application 10-2017-0127716 and 2018.06.01. Korean Patent Application No. 10-2018-0063124, all of which are incorporated herein by reference in their entirety.

The present invention relates to a polyimide precursor solution having a high solid content and a low viscosity, and a polyimide prepared using the same.

Polyimide (PI) is a polymer having a relatively low crystallinity or mostly amorphous structure. It is easy to synthesize, can form a thin film, and does not need a crosslinking agent for curing. In addition to this, polyimide is a polymeric material that has transparency and rigid chain structure and has excellent heat resistance, chemical resistance, mechanical properties, electrical properties and dimensional stability. It is used in automotive, aerospace, flexible circuit boards, LCD Liquid crystal alignment films, bonding and coating agents, and the like.

Generally, a flexible device is manufactured by applying a polyimide precursor solution onto a carrier substrate, curing the film to form a film, completing the device through a subsequent process, and then removing the completed device from the carrier substrate.

Therefore, the storage stability at room temperature of the polyimide precursor solution is particularly important. If the storage stability of the polyimide precursor solution is poor and the process viscosity is changed, the coating and curing process of the polyimide precursor solution becomes unstable. Polyimic acid, which is a polyimide precursor, is known to have poor storage stability because the carboxylic acid that promotes hydrolysis is adjacent to an amide bond.

On the other hand, a flexible device involving a high-temperature process is required to have high heat resistance. In particular, in the case of an organic light emitting diode (OLED) device using a low temperature polysilicon (LTPS) process, the process temperature may approach 500 ° C. However, at such a temperature, even a polyimide having excellent heat resistance tends to undergo thermal decomposition.

Further, in the case where light emitted from the display element is emitted through a film substrate (for example, a bottom emission type organic EL or the like), transparency of the film substrate is required. In particular, it is required to have a high light transmittance in a wavelength region of 400 nm or less, which is a visible light region. Further, when light passes through the retardation film or the polarizing plate, for example, liquid crystal displays, touch panels, and the like are required to have high transparency.

On the other hand, since the imidized polyimide resin has a low solubility, it is difficult to prepare the polyimide resin in a solution state, and its use for coating may be restricted. However, if the solubility is to be improved, the heat resistance can be reduced, and if the heat resistance is further improved, the light transmittance is lowered.

Therefore, there is a need for a polyimide precursor solution which can exhibit excellent chemical resistance and storage stability due to reduced hydrolysis of the polyimide precursor solution for the manufacture of flexible devices, and simultaneously improve heat resistance and transparency while maintaining mechanical properties.

A problem to be solved by the present invention is to provide a polyimide precursor solution having a high solid content and a low viscosity.

Another object of the present invention is to provide a polyimide film produced using the polyimide precursor solution.

Another object of the present invention is to provide a flexible display device comprising the polyimide film.

In order to solve the problems of the present invention,

A polyimide precursor, and a polyimide precursor solution containing an amide-based organic solvent having a positive logarithm (Log P) and a density of 1 g / cm ³ or less.

According to one embodiment, when the solids content of the polyimide precursor solution containing the organic solvent is 10 to 25% by weight, the viscosity may be 7000 cP or less.

According to one embodiment, the organic solvent may comprise dimethylpropionamide (DMPA) or diethylpropionamide (DEPA).

According to one embodiment, the polyimide precursor contained in the polyimide precursor solution may be a polyamic acid having a repeating structure of formula (1).

[Chemical Formula 1]

In Formula 1,

X is a tetravalent organic group selected from the group consisting of aromatic, alicyclic, and aliphatic tetravalent organic groups derived from a tetracarboxylic dianhydride,

Y comprises a divalent organic group selected from the group consisting of aromatic, alicyclic and aliphatic divalent organic groups derived from diamines.

According to one embodiment, X is one divalent organic group selected from the group consisting of the following formulas (2a) to (2g).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

In the above general formulas (2a) to (2g)

R ₃₁ to R ₄₂ each independently represent an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, t-butyl, pentyl or hexyl) A fluoroalkyl group (for example, a fluoromethyl group, a perfluoroethyl group, a trifluoromethyl group, etc.)

Wherein a ₁ is from 0 to 2 integer, b ₁ is in the range of 0 to 4 integer, c ₁ is from 0 to 8 constant, d ₁ and e ₁ are each independently from 0 to 3 an integer, f ₁ and g _1, respectively Independently, an integer of 0 to 4, h ₁ and j ₁ each independently represent an integer of 0 to 3, i ₁ represents an integer of 0 to 4, k ₁ and l ₁ each independently represent an integer of 0 to 4,

Wherein A _1, A _2, A ₃ represents a single bond, -O-, -CR ₄₆ R ₄₇ are each independently -, -C (= O) - , -C (= O) O-, -C (= O) NH-, -S-, -SO ₂ -, phenylene group, and combinations thereof, wherein R ₄₆ and R ₄₇ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (Such as methyl, ethyl, propyl, isopropyl, t-butyl, pentyl and hexyl) and a fluoroalkyl group A methyl group, and the like).

According to one embodiment, Y is a divalent organic group selected from the group consisting of the following formulas (4a) to (4d).

[Chemical Formula 4a]

(4b)

In Formula 4b, L ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n} 1 -, -O (CH 2) n 2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- , or -COO (CH ₂₎ n ₃ OCO- , N ₁ , n ₂ and n ₃ are each an integer of 1 to 10,

[Chemical Formula 4c]

In Formula 4c, L ₂ and L ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, -COO-, - (CH ₂ ) n ₁ -, -O (CH ₂ ) n ₂ O-, -OCH ₂ -C (CH ₃ ) ₂ -CH ₂ O- Or -COO (CH ₂ ) n ₃ OCO-, n ₁ , n ₂ and n ₃ are each an integer of 1 to 10,

[Chemical formula 4d]

In Formula 4d, L _4, L ₅ and L ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 - _{, -C (CF 3) 2 -} , -CONH-, -COO-, - (CH 2) n 1 -, -O (CH 2) n 2 O-, -OCH 2 -C (CH 3) 2 -CH ₂ O- or -COO (CH ₂ ) n ₃ OCO-, n ₁ , n ₂ and n ₃ are each an integer of 1 to 10,

The at least one hydrogen atom contained in the aromatic rings of the general formulas (4a) to (4d) is an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a pentyl group, Or a fluoroalkyl group having 1 to 10 carbon atoms (for example, a fluoromethyl group, a perfluoroethyl group, a trifluoromethyl group, etc.).

According to one embodiment, the polyimide precursor may further comprise a structure of the following formula (6) in the molecular structure.

[Chemical Formula 6]

In the above formula, p and q are molar fractions, and when p + q = 100, p is 70 to 90 and q is 10 to 30.

In order to solve the other problems of the present invention, there is provided a polyimide film produced from the polyimide precursor solution.

According to one embodiment, the transmittance of the polyimide film may be 75% or more in the range of 380 to 780 nm wavelength.

According to one embodiment, the haze of the polyimide film may be 1 or less.

According to one embodiment, the pyrolysis temperature of the polyimide film may be 400 ° C or higher.

According to one embodiment, the polyimide film may have an elongation of 10% or more, a tensile strength of 30 MPa or more, and a tensile modulus of 1 GPa or more.

According to one embodiment, the polyimide film may have a CTE of -20 to 90 ppm / ° C.

The present invention also provides a flexible display device comprising the polyimide film.

The present invention relates to a polyimide precursor having a distribution coefficient (Log P) of positive and a density of 1 g / cm < ³ > Or less, the interaction between polyamic acid, which is a polyimide precursor, and an organic solvent can be relaxed to lower the viscosity of the polyimide precursor solution, and thus a polyimide precursor solution having a high solid content and a low viscosity can be obtained. According to the present invention, the difference in polarity is reduced due to the amphiphilic characteristic of the amide type solvent in which LogP is positive, so that the phase separation phenomenon between the polyamic acid and the organic solvent can be suppressed.

FIGS. 1 and 2 show the results of SEM observation of the cross-section of the films of Comparative Example 1 and Example 1 by FIB (focused ion beam) treatment.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

In the present specification, all the compounds or organic groups may be substituted or unsubstituted, unless otherwise specified. The term " substituted " means that at least one hydrogen atom contained in the compound or organic group is substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, Substituted with a substituent selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, a carboxylic acid group, an aldehyde group, an epoxy group, a cyano group, a nitro group, an amino group, a sulfonic acid group and derivatives thereof.

The polyimide film is one of the materials attracting attention as a flexible display substrate, and the manufacturing process of the polyimide film substrate is as follows. First, a polyamic acid solution as a polyimide precursor solution is coated on a carrier substrate and thermally cured to form a polyimide film on the carrier substrate. Thereafter, a process necessary for device manufacture is performed on the polyimide film, and then the polyimide film is peeled from the carrier substrate to obtain a flexible display. The most important part of this process is the process of forming a polyimide film on a carrier substrate. When the polyamic acid solution is coated on the carrier substrate, it should be coated with low surface roughness without bubbles. However, the polyamic acid has a high polarity, and the polarity of a commonly used solvent (for example, N-methylpyrrolidone) is relatively high, and the polyamic acid solution has a higher viscosity than the solid component due to the interaction between the solvent and the polyamic acid. This makes it very difficult to control the bubbles generated during coating. In addition, since the water absorption rate is high, when the coating is left standing after the coating, moisture is absorbed to cause solution whitening, and when the coating layer in which whitish tack is formed is thermally cured, high surface roughness is obtained, resulting in defects in the display process. Therefore, in order to lower the viscosity of the solution to improve the processability, the solids content can not but be lowered. However, when the solid content is lowered, the specific gravity of the solvent is relatively increased, so that a large amount of solvent evaporates during thermal curing, resulting in a coating failure.

In order to solve the above conventional problems, the present invention provides a polyimide precursor solution comprising a polyimide precursor and an amide-based organic solvent having a positive logarithm (Log P) and a density of 1 g / cm ³ or less.

The LogP can be calculated using the ACD / LogP module of the ACD / Percepta platform of ACD / Labs. The ACD / LogP module can be calculated using the 2D structure of the molecules using the Quantitative Structure-Property Relationship (QSPR) Based algorithm.

The density of the organic solvent can be measured can be less than 1g / cm ^3, a density of 1 g / cm ³ or more when having a value, the higher the relative viscosity can reduce the process efficiency with a standard measuring method of ASTM D1475.

INDUSTRIAL APPLICABILITY The present invention can reduce the polarity difference between the polyamic acid and the organic solvent due to the amphiphilic property of the amide-based solvent having the positive logarithm (Log P), and can suppress the phase separation phenomenon between the polyamic acid and the organic solvent have.

The present invention is characterized in that an amide organic solvent having a positive LogP value and a density of 1 g / cm ³ or less is used as a polymerization solvent for preparing a polyimide precursor and further contained in a polyimide precursor solution, The viscosity can be lowered. Specifically, the viscosity of the polyimide precursor solution according to the present invention may be 7,000 cP or less, preferably 6,000 cP or less, and more preferably 5,000 cP or less at the solid content level.

If the viscosity of the polyimide precursor solution is high, the efficiency of defoaming is lowered during processing of the polyimide film, so that not only the process efficiency is lowered but also the surface roughness is poor due to the occurrence of bubbles in the film, so that the electrical, optical, have. Accordingly, the present invention can produce a polyimide precursor solution having a low viscosity even under the condition of high solid content by using an amide-based solvent having a positive Log P value and a density of 1 g / cm ³ or less. As a result, The coating defects due to the formation of bubbles can be reduced.

And the LogP is positive, with the density of the solvent 1g / cm ³ or less amide-based organic solvent may be a variety of solvents, especially dimethyl-propionamide (DMPA) or diethyl propionamide (DEPA) is preferred. This is because the polarity is relatively low and the boiling point is low, so the coating property is excellent and the volatility of the solvent is good even at a low temperature, and the amount of the solvent remaining in the film after film formation is low.

On the other hand, when the polyamic acid meets with water to form a salt, clouding occurs and the degree of agglomeration may occur. Curing in this state produces a rough film on the surface. That is, when the haze of the polyimide-based solution coating is too high, the coating property is not good and surface roughness may occur after curing. Such improvement of the opacity may contribute to improvement of surface characteristics after curing.

When the distribution coefficient value is a positive number, it means that the polarity of the solvent is hydrophobic. According to the studies of the inventors of the present invention, when a polyimide precursor solution is prepared using a specific solvent having a positive distribution coefficient, The formation of a salt by an acid and water or a polar organic solvent can be suppressed, and as a result, the haze can be improved. Therefore, the polyimide-based film according to the present invention can have high heat resistance and mechanical properties together with excellent transparency.

On the other hand, in the step of coating the polyimide precursor solution on the glass substrate, dewetting of the solution due to shrinkage of the coating layer at the time of curing or under the condition of leaving the coating solution may occur. Liquid curling of the coating solution causes a variation in the thickness of the film, resulting in a problem that the film is broken due to insufficient bending resistance of the film or the edge is broken at the time of cutting, so that the workability in the process is deteriorated and the yield may be lowered. According to the present invention, when an amide-based solvent having a positive distribution coefficient value is used, the curling of the polyimide precursor solution can be improved.

In addition, the polyimide precursor solution containing a polar solvent having a negative logarithm of Log P may have a scattered coating around the region where the foreign matter exists due to the polarity of the foreign matter when the polarized micro- Cracks or thickness variations may occur. On the other hand, when a hydrophobic solvent having an affinity for Log P is used, coating cracking, thickness change and the like can be reduced or suppressed even when a foreign substance having polarity is introduced.

According to one embodiment, the polyimide precursor may be prepared by polymerizing a tetracarboxylic dianhydride and a diamine, and may include a polyamic acid having a repeating structure of the formula (1).

[Chemical Formula 1]

In Formula 1,

X is a tetravalent organic group selected from the group consisting of aromatic, alicyclic, and aliphatic tetravalent organic groups derived from a tetracarboxylic dianhydride,

Y comprises a divalent organic group selected from the group consisting of aromatic, alicyclic and aliphatic divalent organic groups derived from diamines.

The X may be one quaternary organic group selected from the group consisting of the following formulas (2a) to (2g).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

In the above general formulas (2a) to (2g)

R ₃₁ to R ₄₂ each independently represent an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, t-butyl, pentyl or hexyl) A fluoroalkyl group (for example, a fluoromethyl group, a perfluoroethyl group, a trifluoromethyl group, etc.)

Wherein a ₁ is from 0 to 2 integer, b ₁ is in the range of 0 to 4 integer, c ₁ is from 0 to 8 constant, d ₁ and e ₁ are each independently from 0 to 3 an integer, f ₁ and g _1, respectively Independently, an integer of 0 to 4, h ₁ and j ₁ each independently represent an integer of 0 to 3, i ₁ represents an integer of 0 to 4, k ₁ and l ₁ each independently represent an integer of 0 to 4,

Wherein A _1, A _2, A ₃ represents a single bond, -O-, -CR ₄₆ R ₄₇ are each independently -, -C (= O) - , -C (= O) O-, -C (= O) NH-, -S-, -SO ₂ -, phenylene group, and combinations thereof, wherein R ₄₆ and R ₄₇ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (Such as methyl, ethyl, propyl, isopropyl, t-butyl, pentyl and hexyl) and a fluoroalkyl group A methyl group, and the like).

For example, X may be selected from the group consisting of the tetravalent organic groups represented by the following formulas (3a) to (3s).

The aromatic tetravalent organic group represented by any one of the above formulas (3a) to (3s) is a compound wherein at least one hydrogen atom present in the tetravalent organic group is an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, , A pentyl group and a hexyl group) or a fluoroalkyl group having 1 to 10 carbon atoms (for example, a fluoromethyl group, a perfluoroethyl group, a trifluoromethyl group, etc.), a hydroxyl group, a sulfonic acid group and a carboxylic acid group Lt; / RTI > group.

Wherein Y ₂ is to have one or two selected from the group consisting of Formula 4a to 4d can be an organic group.

[Chemical Formula 4a]

(4b)

In Formula 4b, L ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n} 1 -, -O (CH 2) n 2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- , or -COO (CH ₂₎ n ₃ OCO- And n ₁ , n ₂ and n ₃ are integers of 1 to 10, respectively.

[Chemical Formula 4c]

In Formula 4c, L ₂ and L ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, -COO-, - (CH ₂ ) n ₁ -, -O (CH ₂ ) n ₂ O-, -OCH ₂ -C (CH ₃ ) ₂ -CH ₂ O- Or -COO (CH ₂ ) n ₃ OCO-, and n ₁ , n ₂ and n ₃ are integers of 1 to 10, respectively.

[Chemical formula 4d]

In Formula 4d, L _4, L ₅ and L ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 - _{, -C (CF 3) 2 -} , -CONH-, -COO-, - (CH 2) n 1 -, -O (CH 2) n 2 O-, -OCH 2 -C (CH 3) 2 -CH ₂ O- or -COO (CH ₂ ) n ₃ OCO-, and n ₁ , n ₂ and n ₃ are integers of 1 to 10, respectively.

For example, Y may be selected from the group consisting of divalent organic groups represented by the following formulas (5a) to (5p).

At least one hydrogen atom in the divalent group of the general formulas (5a) to (5p) is an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a pentyl group, (For example, a phenyl group, a naphthalenyl group and the like) having 6 to 12 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms such as a fluoromethyl group, a perfluoroethyl group and a trifluoromethyl group, A sulfonic acid group, and a carboxylic acid group.

Further, the polyimide precursor may further include the following structure within the structure,

[Chemical Formula 6]

In the above formula, p and q are molar fractions, and when p + q = 100, p is 70 to 90 and q is 10 to 30.

For example, the siloxane structure of Formula 6 may be formed by further including a diamine of Formula 7 as a polymerization component.

(7)

According to one embodiment, the diamine compound having the structure of Formula 7 has a molecular weight of 4000 g / mol or more, 4200 g / mol or 4400 g / mol, or 6000 g / mol or less, or 5,500 g / . Here, the molecular weight means the weight average molecular weight, and the molecular weight can be calculated by calculating the amine equivalent using NMR analysis or acid-base titration.

The reaction of the tetracarboxylic dianhydride and the diamine can be carried out by a usual polyimide precursor polymerization method such as solution polymerization. Specifically, after the diamine is dissolved in an organic solvent, the tetracarboxylic acid may be subjected to a polymerization reaction by adding an anhydride. The reaction can be carried out under an inert gas or a nitrogen stream and can be carried out under anhydrous conditions.

The polymerization reaction may be carried out at a temperature of -20 캜 to 60 캜, preferably 0 to 45 캜. If the reaction temperature is too high, the reactivity may become high and the molecular weight may become large, and the viscosity of the precursor composition may increase, which may be unfavorable in the process.

In addition, the molecular weight of the polymerized polyamic acid may be 50,000 to 200,000 g / mol, or 60,000 to 150,000 g / mol.

Next, the polyimide precursor obtained as a result of the polymerization reaction is imidized to prepare a transparent polyimide film. At this time, the imidization process may be a chemical imidization or thermal imidization process. Preferably, the polyimide precursor solution is coated on a substrate and then heat-treated to imidize the polyamic acid.

The polyimide precursor solution may be in the form of a solution in which the polyimide precursor is dissolved in an organic solvent. For example, when the polyimide precursor is synthesized in an organic solvent, the solution may be the reaction solution to be obtained, or the reaction solution may be diluted with another solvent. When the polyimide precursor is obtained as a solid powder, it may be a solution prepared by dissolving the polyimide precursor in an organic solvent.

A method for producing a film with a polyimide precursor solution according to the present invention comprises:

Applying the polyimide precursor solution onto a substrate;

And heat treating the applied polyimide precursor solution.

In this case, the substrate may be glass, metal substrate, plastic substrate, or the like without any particular limitation. Among these, the polyimide precursor is excellent in thermal and chemical stability during the imidation and curing process, A glass substrate that can be easily separated without damage to the subsequently formed polyimide-based film may be desirable.

Specific examples of the coating method include a spin coating method, a bar coating method, a roll coating method, an air-knife method, a gravure method, a reverse roll method, a kiss roll method, a doctor blade method, A spray method, a dipping method, a brushing method, or the like may be used. Of these, it is more preferable to carry out the continuous process and to perform the casting method which can increase the imidization rate of the polyimide.

The polyimide precursor solution may also be applied over the substrate to a thickness range such that the final polyimide film has a thickness suitable for the display substrate.

Specifically, it may be applied in an amount such that the thickness is 10 to 30 mu m. After application of the polyimide precursor solution, a drying process to remove the solvent present in the polyimide precursor solution prior to the curing process may optionally be further performed.

The drying process may be carried out according to a conventional method, specifically at a temperature of 140 ° C or lower, or 80 ° C to 140 ° C. If the drying temperature is lower than 80 캜, the drying process becomes longer. If the drying temperature is higher than 140 캜, the imidization rapidly proceeds to make it difficult to form a polyimide film having a uniform thickness.

The polyimide precursor solution is applied to a substrate and heat-treated on an IR oven, a hot air oven or a hot plate. The heat treatment temperature may be in the range of 300 to 500 ° C, preferably 320 to 480 ° C, Or may be performed in a multi-step heating process. The heat treatment process may be conducted for 20 to 70 minutes, preferably 20 to 60 minutes.

The organic solvent contained in the polyimide precursor solution of the present invention may be used is the same as the organic solvent used in the synthesis reaction, the organic solvent is the LogP is positive, and a density of 1g / cm ³ or less amide-based organic For example, a solvent such as dimethyl propionamide (DMPA) or diethyl propionamide (DEPA).

The polyimide-based film may have a haze of 1 or less, preferably 0.9 or less, or 0.7 or less, more preferably 0.5 or less, and the transparency is improved. At this time, the thickness of the polyimide film may be 8 to 15 탆, preferably 10 to 12 탆.

Also, the transmittance for light having a wavelength of 380 to 760 nm in a film thickness range of 5 to 30 占 퐉 may be 70% or more.

For example, the polyimide film according to the present invention can be manufactured by heating and cooling at a temperature ranging from 100 ° C to 450 ° C in a range of n + The thermal expansion coefficient after one run may have a value of -20 to 90 ppm / 占 폚, and the thermal decomposition temperature Td_1% at which the weight is reduced by 1% may be 400 占 폚 or more or 500 占 폚 or more.

The polyimide-based film has a tensile modulus of at least about 1 GPa or at least 3 GPa, a tensile strength of at least about 30 MPa, at least about 100 MPa, or at least about 150 MPa, and a maximum elongation elongation of about 15%, or about 10% or more.

Accordingly, the polyimide-based film can be applied to display substrates and devices. Specifically, the device may be any solar cell having a flexible substrate (e.g., a flexible solar cell), organic light emitting diode (OLED) lighting (e.g., flexible OLED lighting) Device, or an organic electroluminescent device having a flexible substrate, an electrophoretic device, or an LCD device.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

The solvents used in Examples and Comparative Examples of the present invention are shown in Table 1.

	DMPA	DEPA	DMAc	NMP
Boiling point (bp) ( o C)	175	194	166	202
Flash point ( o C)	65.8 ± 9.65	73.6 ± 9.65	63.8 ± 9.6	86.1 ± 0.0
Pka	-0.41 + - 0.70	-0.41 + - 0.70	-0.41 + - 0.70	-0.41 ± 0.20
Density (g / cm 3)	0.876 + 0.06	0.870 + 0.06	0.880 + 0.06	1.029 + 0.06
Log P	0.256 + 0.249	1.275 + 0.249	-0.253 + 0.249	-0.637 + 0.349
Vapor pressure (Torr)	1.12	0.444	1.81	0.299

In Table 1 above, the English abbreviations have the following meanings:

DMPA: Dimethylpropionamide

DEPA: Diethylpropionamide

DMAc: Dimethylacetamide

NMP: 1-Methyl-2-pyrrolidone

The viscosity of the polyimide precursor solution was measured at 25 캜 with a Brookfield rotational viscometer.

The weight average molecular weight of the polyamic acid was measured using Gel Permeation Chromatography (GPC) and eluent (THF: DMF 50:50 by volume)

≪ Example 1 >

299 g (0.091 mol) of TFMB (2,2'-bis (trifluoromethyl) -4,4'-biphenyl diamine) was dissolved in 279 g of DMPA in a reactor through which nitrogen gas flow was flowing, . 20 g (0.091 mol) of PMDA (Pyromellitic Dianhydride) was added to the TFMB solution at the same temperature, and the solution was dissolved for a predetermined time and stirred. DMPA was added so that the solid concentration of the polyimide precursor solution prepared from the reaction was 12 wt%. The resulting polyimide precursor solution had a viscosity of 5,010 cP and a weight average molecular weight of the polyimide precursor, i.e., the polymerized polyamic acid, was 101,000 g / mol.

≪ Examples 2 to 10 &

A polyimide precursor solution was prepared in the same manner as in Example 1 except that the tetracarboxylic acid dianhydride and diamine shown in Table 2 were used. The viscosity of the polyimide precursor solution and the molecular weight of the polyamic acid were measured in Table 2 Respectively.

Example No. 2.	Water	Diamine	menstruum	Solid content (wt%)	Viscosity (cP)	Mw
One	PMDA	TFMB	DMPA	12	5010	101,000
2	BPAF	TFMB	DMPA	12	3200	70,500
3	ODPA	TFMB	DMPA	12	4600	97,100
4	TBIS-BAN	TFMB	DMPA	12	3900	93,000
5	6FDA	TFMB	DMPA	12	5100	78,000
6	PMDA-HS	TFMB	DMPA	12	4500	79,000
7	TAHQ	TFMB	DMPA	12	4800	101,000
8	DSDA	TFMB	DMPA	12	3600	89,000
9	BPDA	PDA	DMPA	12	6800	100,000
10	BPDA	TFMB	DMPA	12	6700	107000

In Table 2 above, the English abbreviations have the following meanings:

PMDA: pyromellitic anhydride

BPFA: 9,9'-bis (3,4-dicaroxyphenyl) fluorene dianhydride

ODPA: 4,4'-oxydiphthalic anhydride

TBIS-BAN: (N, N'- (9H-Fluoren-9-ylidene di-4,1-phenylene) bis [1,3- dihydro- 1,3- dioxo-5-isobenzofurancarboxamide]

6FDA: 4,4 '- (Hexafluoroisopropylidene) diphthalic anhydride

PMDA-HS: 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride

TAHQ: hydroquinone bis (trimellitate anhydride)

DSDA: 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride

TFMB: 2,2'-bis (trifluoromethyl) benzidine

PDA: para-phenylenediamine

BPDA: 3,3 ', 4,4' '- Biphenyltetracarboxylic dianhydride

≪ Example 11 >

299 g (0.091 mol) of TFMB (2,2'-bis (trifluoromethyl) -4,4'-biphenyl diamine) was dissolved in a reactor in which nitrogen gas flow was carried out and 279 g of DEPA was charged. . 20 g (0.091 mol) of PMDA (Pyromellitic Dianhydride) was added to the TFMB solution at the same temperature, and the solution was dissolved for a predetermined time and stirred. DMPA was added so that the solid concentration of the polyimide precursor solution prepared from the reaction was 12 wt%. The resulting polyimide precursor solution had a viscosity of 4300 cP and a weight average molecular weight of the polymerized polyamic acid of 99,000 g / mol.

≪ Examples 12 to 20 &

A polyimide precursor solution was prepared in the same manner as in Example 11, except that the tetracarboxylic acid dianhydride and diamine shown in Table 3 were used. The viscosity of the polyimide precursor solution and the molecular weight of the polyamic acid were measured in the same manner as in Example 11, Respectively.

Example No.	Water	Diamine	menstruum	Solid content (wt%)	Viscosity (cP)	Mw
11	PMDA	TFMB	DEPA	12	4300	99,000
12	BPAF	TFMB	DEPA	12	2900	72,000
13	ODPA	TFMB	DEPA	12	3250	95,000
14	TBIS-BAN	TFMB	DEPA	12	3020	91,200
15	6FDA	TFMB	DEPA	12	4600	77,000
16	PMDA-HS	TFMB	DEPA	12	3810	73,000
17	TAHQ	TFMB	DEPA	12	4200	98,900
18	DSDA	TFMB	DEPA	12	3050	81,000
19	BPDA	PDA	DEPA	12	4800	107,000
20	BPDA	TFMB	DEPA	12	4600	108,000

≪ Comparative Example 1 &

299 g (0.091 mol) of TFMB (2,2'-bis (trifluoromethyl) -4,4'-biphenyl diamine) was dissolved in 279 g of DMAc in a reactor through which nitrogen gas flow was flowing, . 20 g (0.091 mol) of PMDA (Pyromellitic Dianhydride) was added to the TFMB solution at the same temperature, and the solution was dissolved for a predetermined time and stirred. DMAc was added so that the solid concentration of the polyimide precursor solution prepared from the reaction was 12 wt%. As a result, the prepared polyimide precursor solution had a viscosity of 12,000 cP and a weight average molecular weight of the polymerized polyamic acid was 100,400 g / mol.

≪ Comparative Examples 2 to 10 &

A polyimide precursor solution was prepared in the same manner as in Comparative Example 1, except that the tetracarboxylic acid dianhydride and diamine shown in Table 4 were used. The viscosity of the polyimide precursor solution and the molecular weight of the polyamic acid were measured in Table 4 Respectively.

Comparative Example No. 1	Water	Diamine	menstruum	Solid content (wt%)	Viscosity (cP)	Mw
One	PMDA	TFMB	DMAc	12	12,000	100,400
2	BPAF	TFMB	DMAc	12	10,600	90,500
3	ODPA	TFMB	DMAc	12	8,100	96,500
4	TBIS-BAN	TFMB	DMAc	12	8,200	94,500
5	6FDA	TFMB	DMAc	12	8,900	98,000
6	PMDA-HS	TFMB	DMAc	12	7,100	76,500
7	TAHQ	TFMB	DMAc	12	8,600	100,000
8	DSDA	TFMB	DMAc	12	7,300	91,000
9	BPDA	PDA	DMAc	12	10,090	102,000
10	BPDA	TFMB	DMAc	12	16,000	996,000

≪ Comparative Example 11 &

299 g (0.091 mol) of TFMB (2,2'-bis (trifluoromethyl) -4,4'-biphenyl diamine) was dissolved in 279 g of NMP in a reactor through which nitrogen gas flow was flowing, . 20 g (0.091 mol) of PMDA (Pyromellitic Dianhydride) was added to the TFMB solution at the same temperature, and the solution was dissolved for a predetermined time and stirred. NMP was added so that the solids concentration of the polyimide precursor solution prepared from the reaction was 12 wt%. As a result, the viscosity of the prepared polyimide precursor solution was 16,000 cP, and the molecular weight of the polymerized polyamic acid was 109,000 g / mol.

≪ Comparative Examples 12 to 20 &

A polyimide precursor solution was prepared in the same manner as in Comparative Example 11, except that the tetracarboxylic acid dianhydride and diamine shown in Table 5 were used. The viscosity of the polyimide precursor solution and the molecular weight of the polyamic acid were measured in Table 5 Respectively.

Comparative Example No. 1	Water	Diamine	menstruum	Solid content (wt%)	Viscosity (cP)	Mw
11	PMDA	TFMB	NMP	12	16,000	109,000
12	BPAF	TFMB	NMP	12	7,300	87,000
13	ODPA	TFMB	NMP	12	9,800	102,000
14	TBIS-BAN	TFMB	NMP	12	8,900	99,000
15	6FDA	TFMB	NMP	12	8,300	82,000
16	PMDA-HS	TFMB	NMP	12	8,200	80,500
17	TAHQ	TFMB	NMP	12	9,700	103,000
18	DSDA	TFMB	NMP	12	8,900	93,000
19	PMDA	PDA	NMP	12	15,000	108,000
20	BPDA	TFMB	NMP	12	19,500	110,000

As can be seen from the results of Examples 1 to 20 and Comparative Examples 1 to 20, it can be seen that the polyimide precursor solution containing the organic solvent according to the present invention has a low viscosity even under the condition of high solid content. On the other hand, the polyimide precursor solution of the comparative example is a polar solvent having a negative distribution coefficient, and the viscosity thereof is formed to be higher than the viscosity of the embodiment at the same solid concentration. This is because the defoaming effect of the bubbles in the solution during the production of the polyimide film is Which means that pores can be generated due to defective defoaming in the film after coating.

<Experimental Example 1>

Figs. 1 and 2 show the results of SEM observation of the film cross sections of Comparative Example 1 and Example 1 treated with FIB. It can be seen that micro-sized pores exist in the cross-section of the film of Comparative Example 1 in which the defoaming effect is lowered due to the relatively high viscosity of the polyimide precursor solution, while pores are not present in the cross-section of the film of Example 1. [

<Experimental Example 2>

The polyimide precursor solutions prepared in Examples 1, 2, 5, 9 and 10 were spin-coated onto glass substrates. The glass substrate coated with the polyimide precursor solution was placed in an oven and heated at a rate of 2 DEG C / min. The glass substrate was cured at 80 DEG C for 15 minutes, at 150 DEG C for 30 minutes, at 220 DEG C for 30 minutes, and at 380 DEG C for 1 hour The process was carried out. After completion of the curing process, the glass substrate was immersed in water to remove the film formed on the glass substrate, and then dried in an oven at 100 DEG C to prepare a polyimide film.

The CTE, thermal decomposition temperature, elongation, tensile strength, tensile modulus and transmittance of the prepared film were measured by the following methods, and the results are shown in Table 6.

<CTE measurement>

Cut the film to 5 x 20 mm and prepare the sample and load the sample using the accessories. The actual measured film length was equal to 16 mm. The film was pulled up at a rate of 5 ° C / min in a temperature range of 100 ° C to 400 ° C, and then cooled at a rate of 4 ° C / min in a temperature range of 400 ° C to 100 ° C. The rate of thermal expansion change when cooling at the speed was measured by TMA (Q400, TA company).

&Lt; Measurement of thermal decomposition temperature Td_1%

The pyrolysis temperature was measured by the method of ISO 11359.

<Measurement of elongation, tensile strength and tensile modulus>

Zwick's UTM was used to measure the mechanical properties (tensile modulus, tensile strength, elongation) of the film. The film was cut to a width of 5 mm or more and a length of 60 mm or more, and the distance between the grips was set to 40 mm, and the sample was pulled at a speed of 20 mm / min.

<Measurement of transmittance>

The transmittance was measured by a transmittance meter (model name HR-100, manufactured by Murakami Color Research Laboratory) according to JIS K 7105.

	unit	Example 1	Example 2	Example 5	Example 9	Example 10
		PMDA_TFMB	BPAF_TFMB	6FDA_TFMB	BPDA_PDA	BPDA_TFMB
Solid concentration	wt.%	12	12	12	12	12
Viscosity	cP	5010	3200	5100	6800	6700
Molecular Weight	Mw	101,000	70,500	78,000	100,000	107,000
thickness	㎛	10	10	10	10	10
CTE (100 ~ 450 o C1 st cooling)	ppm / ° C	-17	75 @ ~ 350 ° C	70 ~ 300 ° C	3.3	20 @ ~ 300 ° C
Td_1%	℃	535	530	501	565	546
Elongation	%	23	15	20	15.4	20
The tensile strength	Mpa	290	150	190	343.3	230
Tensile modulus	Gpa	7.5	3.2	3.5	9.3	4.6
Transmittance (T avar. 380-780 nm)	%	80	88	88	79	89

From the results shown in Table 6, it can be seen that the polyimide film having excellent thermal resistance as well as excellent mechanical properties and permeability can be obtained at a thermal decomposition temperature of 400 DEG C or higher, or even 500 DEG C or higher.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (14)

1. A polyimide precursor and, 25 ℃ partition coefficient (Log P) positive and the polyimide precursor solution to a density of the organic solvent include amide-based than 1g / cm ^3.
2. The method according to claim 1,

   Wherein the polyimide precursor solution containing the organic solvent has a viscosity of 7000 cP or less when the solids content of the polyimide precursor solution is 10 to 25% by weight.
3. The method according to claim 1,

   Wherein the organic solvent comprises dimethyl propionamide (DMPA) or diethyl propionamide (DEPA).
4. The method according to claim 1,

   Wherein the polyimide precursor comprises a polyamic acid having a repeating structure of Formula (1): &lt; EMI ID =

   [Chemical Formula 1]

   

   X is a tetravalent organic group selected from the group consisting of aromatic, alicyclic, and aliphatic tetravalent organic groups derived from a tetracarboxylic dianhydride,

   Y comprises a divalent organic group selected from the group consisting of aromatic, alicyclic and aliphatic divalent organic groups derived from diamines.
5. 5. The method of claim 4,

   Wherein X is one quadrivalent organic group selected from the group consisting of the following formulas (2a) to (2g):

   (2a)

   

   (2b)

   

   [Chemical Formula 2c]

   

   (2d)

   

   [Formula 2e]

   

   (2f)

   

   [Chemical Formula 2g]

   

   In the above general formulas (2a) to (2g)

   Each of R ₃₁ to R ₄₂ is independently an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms,

   Wherein a ₁ is from 0 to 2 integer, b ₁ is in the range of 0 to 4 integer, c ₁ is from 0 to 8 constant, d ₁ and e ₁ are each independently from 0 to 3 an integer, f ₁ and g _1, respectively Independently, an integer of 0 to 4, h ₁ and j ₁ each independently represent an integer of 0 to 3, i ₁ represents an integer of 0 to 4, k ₁ and l ₁ each independently represent an integer of 0 to 4,

   Wherein A _1, A _2, A ₃ represents a single bond, -O-, -CR ₄₆ R ₄₇ are each independently -, -C (= O) - , -C (= O) O-, -C (= O) NH-, -S-, -SO ₂ -, phenylene and combinations thereof, wherein R ₄₆ and R ₄₇ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms And a fluoroalkyl group.
6. 5. The method of claim 4,

   Wherein Y is a divalent organic group selected from the group consisting of the following formulas (4a) to (4d):

   [Chemical Formula 4a]

   

   (4b)

   

   In Formula 4b, L ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n} 1 -, -O (CH 2) n 2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- , or -COO (CH ₂₎ n ₃ OCO- , N ₁ , n ₂ and n ₃ are each an integer of 1 to 10,

   [Chemical Formula 4c]

   

   In formula 4c, L ₂ and L ₃ may be the same or different from each other, and each independently a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, _{-C (CF 3) 2 -,} -CONH-, -COO-, - (CH 2) n 1 -, -O (CH 2) n 2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- or -COO (CH ₂ ) n ₃ OCO-, n ₁ , n ₂ and n ₃ are each an integer of 1 to 10,

   [Chemical formula 4d]

   

   L ₄ , L ₅ and L ₆ may be the same or different and each independently represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) _{2 -, -C (CF 3)} 2 -, -CONH-, -COO-, - (CH 2) n 1 -, -O (CH 2) n 2 O-, -OCH 2 -C (CH 3) 2 -CH ₂ O- or -COO (CH ₂ ) n ₃ OCO-, n ₁ , n ₂ and n ₃ are each an integer of 1 to 10,

   The at least one hydrogen atom contained in the aromatic rings of the general formulas (4a) to (4d) may be substituted or unsubstituted with a substituent selected from an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms.
7. The method according to claim 1,

   Wherein the polyimide precursor further comprises a structure of the following formula (6) in the molecular structure:

   [Chemical Formula 6]

   

   In the above formula, p and q are molar fractions, and when p + q = 100, p is 70 to 90 and q is 10 to 30.
8. A polyimide film obtained by curing the polyimide precursor solution according to claim 1.
9. 9. The method of claim 8,

   Wherein the polyimide film has a transmittance of 75% or more in a range of 380 to 780 nm.
10. 9. The method of claim 8,

    Wherein the polyimide film has a haze of 1 or less.
11. 9. The method of claim 8,

    Wherein the polyimide film has a pyrolysis temperature of 400 DEG C or higher.
12. 9. The method of claim 8,

    Wherein the polyimide film has an elongation of 10% or more, a tensile strength of 30 MPa or more, and a tensile modulus of 1 GPa or more.
13. 9. The method of claim 8,

    Wherein the polyimide film has a CTE of -20 to 90 ppm / 占 폚.
14. 9. A flexible display device comprising the polyimide film according to claim 8.

Images